WO2004103942A1 - Process for the hydrocarboxylation of ethylenically unsaturated carboxylic acids - Google Patents
Process for the hydrocarboxylation of ethylenically unsaturated carboxylic acids Download PDFInfo
- Publication number
- WO2004103942A1 WO2004103942A1 PCT/EP2004/050820 EP2004050820W WO2004103942A1 WO 2004103942 A1 WO2004103942 A1 WO 2004103942A1 EP 2004050820 W EP2004050820 W EP 2004050820W WO 2004103942 A1 WO2004103942 A1 WO 2004103942A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- group
- ethylenically unsaturated
- source
- optionally substituted
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/14—Adipic acid
Definitions
- This invention relates to a process for the hydrocarboxylation of an ethylenically unsaturated carboxylic acid, by reacting it with carbon monoxide and a co-reactant selected from the group of water and carboxylic acids, in the presence of a catalyst system including a source of palladium, a bidentate diphosphine and a source of anions, to prepare a dicarboxylic acid.
- a catalyst system including a source of palladium, a bidentate diphosphine and a source of anions
- the present invention provides a process for the hydrocarboxylation of an ethylenically unsaturated carboxylic acid, by reacting it with carbon monoxide and a co-reactant selected from the group of water and carboxylic acids, in the presence of a catalyst system including:
- suitable sources for palladium of component (a) include palladium metal and complexes and compounds thereof, such as palladium salts, for example the salts of palladium and halide acids, nitric acid, sulphuric acid or sulphonic acids; palladium complexes, e.g. with carbon monoxide or acetylacetonate, or palladium combined with a solid material such as an ion exchanger.
- palladium metal and complexes and compounds thereof such as palladium salts, for example the salts of palladium and halide acids, nitric acid, sulphuric acid or sulphonic acids
- palladium complexes e.g. with carbon monoxide or acetylacetonate
- palladium combined with a solid material such as an ion exchanger.
- a salt of palladium and a carboxylic acid is used, suitably a carboxylic acid with up to 12 carbon atoms, such as salts of acetic acid, propionic acid and butanoic acid, or salts of substituted carboxylic acids such as trichloroacetic acid and trifluoroacetic acid.
- a very suitable source is palladium (II) acetate.
- R represents an optionally substituted aromatic group which is linked to the phosphorus atoms via the alkylene groups.
- the aromatic group can be a monocyclic group, such as for example a phenyl group or a polycyclic group, such as for example naphthyl, anthryl or indyl group.
- the aromatic group R contains only carbon atoms, but R can also represent an aromatic group wherein a carbon chain is interrupted by one or more hetero atoms, such as nitrogen, sulphur or oxygen atom in for example a pyridine, pyrrole, furan, thiophene, oxazole or thiazole group.
- the aromatic group R represents a phenyl group.
- the aromatic group is substituted.
- Suitable substituents include groups containing hetero- atoms such as halides, sulphur, phosphorus, oxygen and nitrogen. Examples of such groups include chloride, bromide, iodide and groups of the general formula -O-H, -O-X 2 , -CO-X 2 , -CO-0-X 2 , -S-H, -S-X 2 , -CO-S-X 2 , -NH 2 ,
- X 2 and X 3 independently, represent alkyl groups having from 1 to 4 carbon atoms like methyl, ethyl, propyl, isopropyl and n-butyl.
- X 2 and X 3 independently, represent alkyl groups having from 1 to 4 carbon atoms like methyl, ethyl, propyl, isopropyl and n-butyl.
- the aromatic group is substituted it is preferably substituted with one or more aryl, alkyl or cycloalkyl groups, preferably having from 1 to 10 carbon atoms.
- Suitable groups include, methyl, ethyl, propyl, iso-propyl, butyl and iso-butyl, phenyl and cyclohexyl .
- the aromatic group is non- substituted and only linked to the alkylene groups which connect it with the phosphorus atoms.
- the alkylene groups are connected at adjacent positions, for example the 1 and 2 positions, of the aromatic group.
- the alkylene groups are lower alkylene groups.
- lower alkylene groups is understood alkylene groups comprising from 1 to 4 carbon atoms.
- the alkylene groups can be substituted, for example with alkyl groups, or non-substituted.
- the alkylene groups are non-substituted. More preferably the alkylene groups are unsubstituted methylene or ethylene groups, most preferably methylene groups.
- R1, R 2 , R5 and R ⁇ can independently represent organic groups containing a tertiary carbon atom through which the group is linked to the phosphorus atom.
- the groups R1, R 2 , R ⁇ and R° are only connected to each other via the phosphorus atom.
- the organic groups preferably have from 4 to 30 carbon atoms, yet more preferably from 4 to 20 carbon atoms, and again more preferably from 4 to 8 carbon atoms.
- the tertiary carbon atom can be substituted with aliphatic, cyclo-aliphatic or aromatic substituents or can form part of a substituted saturated or non-saturated aliphatic ring structure.
- suitable organic groups are tert-butyl, 2- (2-methyl ) - butyl, 2-(2-ethyl)butyl, 2- (2-phenyl) butyl, 2- (2- methyl)pentyl, 2- (2-ethyl) pentyl, 2- (2-methyl-4-phenyl) - pentyl, 1- (1-methyl) cyclohexyl and 1-adamantyl groups, and derivatives of these groups, wherein one or more of the carbon atoms are substituted by heteroatoins .
- the tertiary carbon atom is substituted with alkyl groups, i.e. preferably the organic group is a tertiary alkyl group.
- tert-butyl groups and 1- adamantyl groups are most preferred.
- the groups R ⁇ , R 2 , R ⁇ and R ⁇ represent the same tertiary alkyl groups, most preferably groups R 1 , R 2 , R ⁇ and R ⁇ are tert-butyl groups.
- An especially preferred bidentate diphosphine is 1,2-bis [ (di (tert-butyl) phosphinomethyl] benzene (also known as bis [di (tert-butyl) phosphino]-o-xylene) .
- the ratio of moles of bidentate diphosphine, i.e. catalyst component (b) , per mole atom of palladium, i.e. catalyst component (a), ranges from 0.5 to 20, preferably from 1 to 10.
- suitable anions, i.e. component (c) of the catalyst system include anions of phosphoric acid, sulphuric acid, sulphonic acids, carboxylic acids and halogenated carboxylic acids such as trifluoroacetic acid.
- Sulphonic acids are in particular preferred, for example trifluoror ⁇ ethanesulphonic acid, p-toluene- sulphonic acid and 2, 4, 6-trimethylbenzene sulphonic acid, 2-hydroxypropane-2-sulphonic acid, tert-butyl sulphonic acid and methyl sulphonic acid.
- Especially preferred sulphonic acids are methyl sulphonic acid, tert-butyl sulphonic acid, 2, 4, 6-trimethylbenzene sulphonic acid.
- Yet more preferred anions are anions of acids having a pKa of above 3, such as carboxylic acids.
- Suitable carboxylic acids are those having from 2-20 carbon atoms, such as acetic acid, propionic acid butyric acid, pentanoic acid and nonanoic acid.
- the acid corresponding to the unsaturated carboxylic acid reactant can be used as catalyst component (c) .
- the reactant is 3-pentenoic acid, this same acid can be conveniently used as the catalyst component (c) as well.
- the carboxylic acid may also be a mixture of the reactant and its structural isomers. In the case the reactant is 3-pentenoic acid, these include the 2- and 4-pentenoic acid other than the cis-3-pentenoic acid and/or trans-3-pentenoic acid.
- Catalyst component (c) can also be an ion exchanging resin containing sulphonic acid groups or carboxylic acid groups.
- the molar ratio of the source of anions and palladium, i.e. catalyst components (c) and (b) is suitably between 2:1 and 10 ⁇ :1 and more preferably between 2:1 and lOAl.
- the process may optionally be carried out in the presence of a solvent.
- the ethylenically unsaturated carboxylic acid has at least 3 carbon atoms.
- the ethylenically unsaturated carboxylic acid has from 4 to 20 and more preferably from 4 to 14 carbon atoms, such as acrylic acid, 2-cis -pentenoic acid and/or 2-trans-pentenoic acid or a mixture thereof, 3-cis pentenoic acid and/or
- the ethylenically unsaturated carboxylic acid can be substituted or non- substituted.
- the co-reactant is water, a carboxylic acid or a combination thereof.
- the product obtained will be dibasic carboxylic acid.
- Mono anhydric carboxylic acids are obtained inasmuch as the co-reactant is a carboxylic acid.
- the carboxylic acid co-reactant has the same number of carbon atoms as the ethylenically unsaturated carboxylic acid reactant.
- the ratio (v/v) of ethylenically unsaturated carboxylic acid and water can vary between wide limits and suitably lies in the range of 1:0.1 to 1:10, more suitably from 2:1 to 1:2.
- the hydrocarboxylation reaction according to the present invention is carried out at moderate temperatures and pressures. Suitable reaction temperatures are in the range of 50-250 °C, preferably in the range of 80-150 °C.
- the reaction pressure is usually at least atmospheric. Suitable pressures are in the range of 0,1 to 15 MPa (1 to 150 bar), preferably in the range of 0,5 to 8,5 MPa (5 to 85 bar) .
- Carbon monoxide partial pressures in the range of 0,1 to 6,5 MPa (1-65 bar) are preferred.
- the carbon monoxide can be used in its pure form or diluted with an inert gas such as nitrogen, carbon dioxide or noble gases such as argon.
- the addition of limited amounts of hydrogen such as 3 to 20 mol% of the amount of carbon monoxide used, promotes the hydrocarbonylation reaction.
- the use of higher amounts of hydrogen tends to cause the undesirable hydrogenation of the ethylenically unsaturated carboxylic acid reactant.
- the amount of catalyst used in the process is not critical. Good results are obtained when the amount of palladium is in the range of 10 _ 7 o lO- ⁇ gram atom per mole of ethylenically unsaturated compound. Preferably this amount is in the range of 10 ⁇ 5 to 5.10 "2 gram atom per mole.
- Examples 1-3 hydrocarboxylation of 3-pentenoic acid to adipic acid
- a solution of the preformed catalyst composition of 0.1 mol palladium acetate, 0.5 mol of the ligand and 1 mol methane sulphonic acid in 10 ml of acetone was added and the autoclave was closed and evacuated.
- the ligand in Examples 1-3 was 1,2-bis [di (tert-butyl) phosphinomethyl] benzene and in
- the autoclave was pressurized with CO to 3 MPa and heated at 90 or 105 °C for 10 hr.
- the contents consisted of a slurry of adipic acid, diglyme and pentenoic acid.
- the initial carbonylation rate (mol per mol Pd per hour) of this batch operation is defined for Examples 1-3 as the mean rate of carbon monoxide consumption (pressure drop) over the first 30% substrate consumption.
- the initial carbonylation rate is defined as the mean rate of CO consumption over the first two hours.
- the liquid phase of the slurry of Examples 2 and 3 was analysed with G1C, and showed a pentenoic acid conversion to adipic acid of more than 90 mol% in both cases. Also, 15 g and 17 g respectively of white adipic acid was recovered by filtration at room temperature.
- a mixed substrate of the following composition was used:
- the reaction mixture was almost completely composed of solid adipic acid.
- THF was added to form a slurry of adipic acid in THF.
- the THF phase was analysed by GLC and the conversion of pentenoic acid was determined from the residual pentenoic acid. In all experiments pentenoic acid conversion was higher than 90%. Selectivity to adipic acid was >95%.
- the initial carbonylation rate (mol per mol of Pd per hour) of this batch operation, as presented in Table II, is defined as the mean rate of carbon monoxide consumption (pressure drop) over the first 30% substrate consumption.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/557,403 US7348454B2 (en) | 2003-05-22 | 2004-05-17 | Process for the hydrocarboxylation of ethylenically unsaturated carboxylic acids |
EP04741582A EP1628946A1 (en) | 2003-05-22 | 2004-05-17 | Process for the hydrocarboxylation of ethylenically unsaturated carboxylic acids |
CA002526346A CA2526346A1 (en) | 2003-05-22 | 2004-05-17 | Process for the hydrocarboxylation of ethylenically unsaturated carboxylic acids |
JP2006530201A JP2006528227A (en) | 2003-05-22 | 2004-05-17 | Process for the hydrocarboxylation of ethylenically unsaturated carboxylic acids |
BRPI0410461-7A BRPI0410461A (en) | 2003-05-22 | 2004-05-17 | process for the hydrocarboxylation of an ethylenically unsaturated carboxylic acid |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03076568.9 | 2003-05-22 | ||
EP03076568 | 2003-05-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004103942A1 true WO2004103942A1 (en) | 2004-12-02 |
Family
ID=33462164
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2004/050820 WO2004103942A1 (en) | 2003-05-22 | 2004-05-17 | Process for the hydrocarboxylation of ethylenically unsaturated carboxylic acids |
Country Status (8)
Country | Link |
---|---|
US (1) | US7348454B2 (en) |
EP (1) | EP1628946A1 (en) |
JP (1) | JP2006528227A (en) |
KR (1) | KR20060013546A (en) |
CN (1) | CN1795159A (en) |
BR (1) | BRPI0410461A (en) |
CA (1) | CA2526346A1 (en) |
WO (1) | WO2004103942A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006084892A2 (en) * | 2005-02-11 | 2006-08-17 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of a dicarboxylic acid |
WO2006125801A1 (en) * | 2005-05-27 | 2006-11-30 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of adipic acid from n-pentenoic acid |
WO2011110249A1 (en) | 2010-03-12 | 2011-09-15 | Evonik Degussa Gmbh | Process for preparing linear alpha,omega-dicarboxylic diesters |
CN110423191A (en) * | 2019-07-05 | 2019-11-08 | 常州大学 | A kind of synthetic method of end position carboxylic acid |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG193629A1 (en) * | 2011-03-28 | 2013-11-29 | Agency Science Tech & Res | Synthesis of diacids |
CN114805434A (en) * | 2021-01-18 | 2022-07-29 | 惠州凯特立斯科技有限公司 | Novel tetradentate phosphine ligand compound and synthetic method and application thereof |
CN114835746A (en) * | 2021-02-01 | 2022-08-02 | 惠州凯特立斯科技有限公司 | Novel tetradentate phosphine ligand compound and synthetic method and application thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002048094A1 (en) * | 2000-12-11 | 2002-06-20 | E. I. Du Pont De Nemours And Company | tROCESS FOR MAKING 5-CYANOVALERIC ACID, ADIPIC ACID OR DIMETHYL ADIDPATE |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH026427A (en) * | 1988-06-27 | 1990-01-10 | Idemitsu Kosan Co Ltd | Production of dicarboxylic acid and formylcarboxylic acid |
US6706912B2 (en) | 2000-03-14 | 2004-03-16 | Shell Oil Company | Process for the carbonylation of ethylenically unsaturated compounds |
-
2004
- 2004-05-17 CA CA002526346A patent/CA2526346A1/en not_active Abandoned
- 2004-05-17 BR BRPI0410461-7A patent/BRPI0410461A/en not_active IP Right Cessation
- 2004-05-17 WO PCT/EP2004/050820 patent/WO2004103942A1/en not_active Application Discontinuation
- 2004-05-17 JP JP2006530201A patent/JP2006528227A/en active Pending
- 2004-05-17 KR KR1020057022097A patent/KR20060013546A/en not_active Application Discontinuation
- 2004-05-17 EP EP04741582A patent/EP1628946A1/en not_active Withdrawn
- 2004-05-17 CN CNA2004800141165A patent/CN1795159A/en active Pending
- 2004-05-17 US US10/557,403 patent/US7348454B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002048094A1 (en) * | 2000-12-11 | 2002-06-20 | E. I. Du Pont De Nemours And Company | tROCESS FOR MAKING 5-CYANOVALERIC ACID, ADIPIC ACID OR DIMETHYL ADIDPATE |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006084892A2 (en) * | 2005-02-11 | 2006-08-17 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of a dicarboxylic acid |
WO2006084892A3 (en) * | 2005-02-11 | 2006-12-07 | Shell Int Research | Process for the preparation of a dicarboxylic acid |
WO2006125801A1 (en) * | 2005-05-27 | 2006-11-30 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of adipic acid from n-pentenoic acid |
WO2011110249A1 (en) | 2010-03-12 | 2011-09-15 | Evonik Degussa Gmbh | Process for preparing linear alpha,omega-dicarboxylic diesters |
DE102010002809A1 (en) | 2010-03-12 | 2011-11-17 | Evonik Degussa Gmbh | Process for the preparation of linear alpha, omega-dicarboxylic acid diesters |
CN110423191A (en) * | 2019-07-05 | 2019-11-08 | 常州大学 | A kind of synthetic method of end position carboxylic acid |
CN110423191B (en) * | 2019-07-05 | 2022-03-29 | 常州大学 | Synthesis method of terminal carboxylic acid |
Also Published As
Publication number | Publication date |
---|---|
US20060224015A1 (en) | 2006-10-05 |
US7348454B2 (en) | 2008-03-25 |
CA2526346A1 (en) | 2004-12-02 |
BRPI0410461A (en) | 2006-06-13 |
CN1795159A (en) | 2006-06-28 |
KR20060013546A (en) | 2006-02-10 |
JP2006528227A (en) | 2006-12-14 |
EP1628946A1 (en) | 2006-03-01 |
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